CN107952110A - 一种骨填充材料及制备方法 - Google Patents
一种骨填充材料及制备方法 Download PDFInfo
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- CN107952110A CN107952110A CN201711210072.9A CN201711210072A CN107952110A CN 107952110 A CN107952110 A CN 107952110A CN 201711210072 A CN201711210072 A CN 201711210072A CN 107952110 A CN107952110 A CN 107952110A
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000011049 filling Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 180
- 239000000919 ceramic Substances 0.000 claims abstract description 42
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 23
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical class [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 10
- MMXZSJMASHPLLR-UHFFFAOYSA-N pyrroloquinoline quinone Chemical compound C12=C(C(O)=O)C=C(C(O)=O)N=C2C(=O)C(=O)C2=C1NC(C(=O)O)=C2 MMXZSJMASHPLLR-UHFFFAOYSA-N 0.000 claims description 70
- 239000004568 cement Substances 0.000 claims description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 47
- 229910052725 zinc Inorganic materials 0.000 claims description 47
- 239000011701 zinc Substances 0.000 claims description 47
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- 229920002678 cellulose Polymers 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 27
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 21
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- 239000011575 calcium Substances 0.000 claims description 4
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- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DAYLJWODMCOQEW-TURQNECASA-N NMN zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP(O)([O-])=O)O2)O)=C1 DAYLJWODMCOQEW-TURQNECASA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 201000010814 Synostosis Diseases 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019347 bone phosphate Nutrition 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
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- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002211 flavins Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 210000000578 peripheral nerve Anatomy 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- ADXCEOBGDCQCKM-UHFFFAOYSA-N quinoline-2,3-dione Chemical compound C1=CC=CC2=NC(=O)C(=O)C=C21 ADXCEOBGDCQCKM-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
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Abstract
本发明涉及一种骨填充材料及制备方法。本发明涉及一种含降温剂骨水泥及制备方法。本发明的骨填充材料由硫酸钙固化体和多孔陶瓷组成；在骨水泥液体中引入降温剂，骨水泥固化过程中降温剂与甲基丙烯酸甲脂发生脂交换吸热反应，接枝到PMMA分子链上，由于吸热，降低了MMA聚合反应释放的热量，降低了骨水泥的最高温度，且由于降温剂的加入延长了骨水泥的固化时间，更进一步降低了热量的集中累积，降低骨水泥最高温度。且引入具有抗菌性、生物活性和骨诱导性的三元素全取代磷灰石。本发明制得的骨填充材料具有抗压强度高、注射性好、抗水溃散性好、降解可控等优点，同时还可具有良好的生物活性、相容性和安全性。本发明可用于多种骨折的固定和骨缺损的填充。
Description
技术领域
本发明涉及一种用于骨组织修复的骨填充材料及制备方法，主要用于生物医用材料等领域。
背景技术
人工骨修复是目前治疗骨缺损较为理想的方法。磷酸钙具有良好的生物活性、生物相容性，其中磷灰石是人体硬组织(骨和牙)的无机质的物质组成，其化学成分和晶体结构与脊椎动物骨的矿物成分非常接近，与人体组织有良好的生物相容性，且无毒性，并能与骨组织形成很好的骨性结合。但是羟基磷灰石机械强度低、降解速度慢等缺点在一定程度上限制了其应用。
硫酸钙是一种传统的骨修复材料，以其良好的生物相容性、骨传导性等在骨修复方面具有良好的应用前景。自Dressman首次使用硫酸钙成功治愈骨缺损以来，硫酸钙骨修复材料逐渐发展，硫酸钙不仅临床疗效，生物学性能更加确切、稳定，且为微创治疗骨缺损提供了一种有效途径；但是硫酸钙的成骨活性较弱，仅具有骨传导性，缺乏骨诱导性，且降解较快。植入体内后，降解较快，而机体则需要至少3个月的时间才能修复骨缺损。
理想的骨替代材料必须有与骨形成速率相同的降解速率，且在骨组织周围不产生刺激，且具有一定强度。目前将磷酸钙和硫酸钙作为骨修复材料已经广泛应用，且两者的结合也起到一定的效果，但将磷酸钙烧结的多孔陶瓷与硫酸钙水泥结合制备骨填充材料，并辅以吡咯喹啉醌的研究未有相关报道。
吡咯喹啉醌是一种新辅基，是继黄素核苷酸和烟酰胺核苷酸之后，在膜束缚的细菌脱氢酶中发现的第三种辅基，世界医学界称之为第十四种维生素，作为一种新型水溶性维生素，是一种氧化还原酶辅基。
本发明以磷酸钙为原料，采用浸提法，经高温烧结制备多孔陶瓷材料，再以硫酸钙水泥包裹，制备硫酸钙多孔陶瓷复合骨填充材料，磷酸钙经高温烧结，转变晶相，控制孔的粒度，在经硫酸钙包裹固化，制得降解可控、力学性能高的复合骨填充材料，对于本发明相关内容的研究未见报道。
发明内容
本发明的目的在于提供一种骨填充材料，由内部的多孔陶瓷和外部包裹的硫酸钙固化体组成，并提供一种骨填充材料的制备方法。多孔陶瓷以磷酸钙为原料，经造型、高温烧结造孔、晶相转化制得，硫酸钙固化体为硫酸钙骨水泥固化制得，硫酸钙骨水泥中以吡咯喹啉醌和纤维素为双增强相，增强骨水泥的韧性和水溃散性，提升骨水泥的抗压强度。
骨填充材料具体组成及质量百分含量为40～80％的硫酸钙水泥和20～60％的多孔陶瓷，硫酸钙水泥中硫酸钙质量百分含量为90～99.6％，吡咯喹啉醌为0.2～2％，纤维素为0.2％～8％，多孔陶瓷优选为锌掺杂的双相陶瓷(Zn-HA/Zn-TCP)。
本发明的骨填充材料的制备按照以下步骤：
(1)多孔陶瓷的制备：将30～80％质量分数的磷酸钙与20～70％质量分数的PVA混合均匀，加入到PVA溶液中，制备磷酸钙/PVA浆液；
将磷酸钙/PVA浆液倒入到聚氨酯泡沫中，经反应1～72h，干燥24h，将其制备成圆柱体，在烧结炉中，烧结温度为800～1250℃，烧结时间为3～36h，室温冷却，得到多孔陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为0.5～5％，纤维素占溶液的质量百分含量为0.5～20％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥。
(3)骨填充材料的制备：在成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，再将占骨填充材料质量百分含量为20～60％的多孔陶瓷放入到硫酸钙水泥中，再注入剩余的10～50％的硫酸钙水泥填满磨具并封口，对其加压5～35MPa，持续15～60min，将其取出固化12～36h，在5％RH环境下干燥3～24h得到圆柱体骨填充材料。
步骤(1)中的磷酸钙的粒径为50～150μm。
步骤(1)中的磷酸钙可以是磷酸三钙、磷酸四钙、磷酸氢钙、磷酸八钙、磷灰石、锶磷灰石、锌磷灰石等的一种或多种，优选锌磷灰石，锌磷灰石中，锌占锌钙的摩尔比为0.5～2:10。
步骤(1)中PVA粒径为200～350μm，PVA溶液中PVA的质量百分含量为1～5％。
步骤(1)中圆柱体尺寸为也可以是球体(r为1～2.5mm)、正方体(边a为1～3mm)的一种。
步骤(2)中纤维素优选羟丙基纤维素，优选羟丙基纤维素占溶液的质量百分含量为10～20％，硫酸钙粒径为50～100μm。
步骤(3)中圆柱体骨填充材料尺寸为也可以是正方体(边a为4～6mm)。
本发明的优点在于：以多孔陶瓷为基体，外层包裹硫酸钙固化体制备复合骨填充材料，改善了单纯多孔陶瓷力学性能不足的问题，增强了骨填充材料的水溃散性及韧性，且硫酸钙的快速降解，释放出吡咯喹啉醌、纤维素，增强机体的免疫力，防止感染，并促进骨细胞生长，加速骨修复，防止因硫酸钙降解导致材料的力学强度的衰减。该骨填充材料的抗压强度均在10MPa以上，满足人体松质骨修复的需要。
附图说明
图1：骨填充材料组成示意图；
图2：制备的多孔陶瓷的SEM图；
图3：骨填充材料的抗压强度图。
具体实施方式
下面结合实施例对本发明的内容作进一步的详细说明，但本发明的实施方式不限于此。
骨填充材料组成与质量百分含量为40～80％的硫酸钙水泥和20～60％的锌掺杂双相陶瓷(Zn-HA/Zn-TCP)，其中硫酸钙水泥中硫酸钙为90～99.6％，吡咯喹啉醌为0.2～2％，纤维素为0.2％～8％，制备方法如下：
(1)锌掺杂双相陶瓷的制备：将30～80％质量分数的磷酸钙与20～70％质量分数的PVA混合均匀，加入到PVA溶液中，制备磷酸钙/PVA浆液；
将磷酸钙/PVA浆液倒入到聚氨酯泡沫中，经反应1～72h，干燥24h，将其制备成圆柱体，在烧结炉中，烧结温度为800～1250℃，烧结时间为3～36h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为0.5～5％，纤维素占溶液的质量百分含量为0.5～20％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥。
(3)骨填充材料的制备：在圆柱体成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，再将占骨填充材料质量百分含量为20～60％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的10～50％的硫酸钙水泥填满磨具并封口，对其加压5～35MPa，持续15～60min，将其取出固化12～36h，在5％RH环境下干燥3～24h得到圆柱体骨填充材料。
实施例1
骨填充材料组成与质量百分含量为80％的硫酸钙固化体和20％的锌掺杂双相陶瓷，其中硫酸钙固化体中硫酸钙为91％，吡咯喹啉醌为1％，纤维素为8％。
(1)锌掺杂双相陶瓷的制备：将80％质量分数的锌磷灰石与20％质量分数的PVA混合均匀，加入到PVA溶液中，制备锌磷灰石/PVA浆液；
将锌磷灰石/PVA浆液倒入到聚氨酯泡沫中，经反应1h，干燥24h，将其制备成的圆柱体，在烧结炉中，烧结温度为1150℃，烧结时间为10h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为2.5％，纤维素占溶液的质量百分含量为20％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在圆柱状成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，按照配比将占骨填充材料质量百分含量为20％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的50％的硫酸钙水泥填满磨具并封口，对其加压20MPa，持续30min，将其取出固化12h，在5％RH环境下干燥24h得到圆柱体骨填充材料，尺寸为
圆柱体骨填充材料的组成示意图，如图1所示，内部为多孔陶瓷，外部为硫酸钙固化体。
对制备的多孔陶瓷进行扫描电镜观察，如图2，孔径为100μm以上，最大达500μm。
对制备的骨填充材料进行抗压强度测试，抗压强度测试样为圆柱状(Φ4mm×6mm)，抗压强度平均值为22.23MPa(如附图3-A所示)。
实施例2
骨填充材料组成与质量百分含量为40％的硫酸钙固化体和60％的锌掺杂双相陶瓷，其中硫酸钙固化体中硫酸钙为96％，吡咯喹啉醌为2％，纤维素为2％。
(1)锌掺杂双相陶瓷的制备：将30％质量分数的锌磷灰石与70％质量分数的PVA混合均匀，加入到PVA溶液中，制备锌磷灰石/PVA浆液；
将锌磷灰石/PVA浆液倒入到聚氨酯泡沫中，经反应24h，干燥24h，将其制备成 的圆柱体，在烧结炉中，烧结温度为1250℃，烧结时间为3h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为5％，纤维素占溶液的质量百分含量为5％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在圆柱状成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，按照配比将占骨填充材料质量百分含量为60％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的10％的硫酸钙水泥填满磨具并封口，对其加压35MPa，持续60min，将其取出固化24h，在5％RH环境下干燥12h得到圆柱体骨填充材料，尺寸为
对制备的骨填充材料进行抗压强度测试，抗压强度测试样为圆柱状(Φ4mm×6mm)，抗压强度平均值为25.2MPa(如附图3-B所示)。
实施例3
骨填充材料组成与质量百分含量为70％的硫酸钙固化体和30％的锌掺杂双相陶瓷，其中硫酸钙固化体中硫酸钙为96.8％，吡咯喹啉醌为0.2％，纤维素为4％。
(1)锌掺杂双相陶瓷的制备：将60％质量分数的锌磷灰石与40％质量分数的PVA混合均匀，加入到PVA溶液中，制备锌磷灰石/PVA浆液；
将锌磷灰石/PVA浆液倒入到聚氨酯泡沫中，经反应72h，干燥24h，将其制备成 的圆柱体，在烧结炉中，烧结温度为1000℃，烧结时间为24h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为0.5％，纤维素占溶液的质量百分含量为10％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在圆柱状成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，按照配比将占骨填充材料质量百分含量为30％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的40％的硫酸钙水泥填满磨具并封口，对其加压5MPa，持续15min，将其取出固化36h，在5％RH环境下干燥3h得到圆柱体骨填充材料，尺寸为
对制备的骨填充材料进行抗压强度测试，抗压强度测试样为圆柱状(Φ4mm×6mm)，抗压强度平均值为18.73MPa(如附图3-C所示)。
实施例4
骨填充材料组成与质量百分含量为75％的硫酸钙固化体和25％的锌掺杂双相陶瓷，其中硫酸钙固化体中硫酸钙为94％，吡咯喹啉醌为1％，纤维素为5％。
(1)锌掺杂双相陶瓷的制备：将70％质量分数的锌磷灰石与30％质量分数的PVA混合均匀，加入到PVA溶液中，制备锌磷灰石/PVA浆液；
将锌磷灰石/PVA浆液倒入到聚氨酯泡沫中，经反应10h，干燥24h，将其制备成 的圆柱体，在烧结炉中，烧结温度为800℃，烧结时间为36h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为2.5％，纤维素占溶液的质量百分含量为12.5％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在圆柱状成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，按照配比将占骨填充材料质量百分含量为25％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的45％的硫酸钙水泥填满磨具并封口，对其加压25MPa，持续35min，将其取出固化24h，在5％RH环境下干燥24h得到圆柱体骨填充材料，尺寸为
对制备的骨填充材料进行抗压强度测试，抗压强度测试样为圆柱状(Φ4mm×6mm)，抗压强度平均值为21.38MPa(如附图3-D所示)。
实施例5
骨填充材料组成与质量百分含量为50％的硫酸钙固化体和50％的锌掺杂双相陶瓷，其中硫酸钙固化体中硫酸钙为97.8％，吡咯喹啉醌为1％，纤维素为0.2％。
(1)锌掺杂双相陶瓷的制备：将65％质量分数的锌磷灰石与35％质量分数的PVA混合均匀，加入到PVA溶液中，制备锌磷灰石/PVA浆液；
将锌磷灰石/PVA浆液倒入到聚氨酯泡沫中，经反应12h，干燥24h，将其制备成 的圆柱体，在烧结炉中，烧结温度为1100℃，烧结时间为5h，室温冷却，得到锌掺杂双相陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为2.5％，纤维素占溶液的质量百分含量为0.5％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在圆柱状成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，按照配比将占骨填充材料质量百分含量为50％的锌掺杂双相陶瓷放入到硫酸钙水泥中，再注入剩余的20％的硫酸钙水泥填满磨具并封口，对其加压25MPa，持续20min，将其取出固化12h，在5％RH环境下干燥24h得到圆柱体骨填充材料，尺寸为
对制备的骨填充材料进行抗压强度测试，抗压强度测试样为圆柱状(Φ4mm×6mm)，抗压强度平均值为14.69MPa(如附图3-E所示)。
Claims (9)
1.一种骨填充材料，其特征在于，骨填充材料组成与质量百分含量为40～80％的硫酸钙水泥和20～60％的多孔陶瓷。
2.如权利要求1所述的骨填充材料，其特征在于，硫酸钙水泥中硫酸钙质量百分含量为90～99.6％，吡咯喹啉醌为0.2～2％，纤维素为0.2％～8％；多孔陶瓷为锌掺杂双相陶瓷。
3.如权利要求1所述的骨填充材料的制备方法，其特征在于，制备步骤如下：
(1)多孔陶瓷的制备：将30～80％质量分数的磷酸钙与20～70％质量分数的PVA混合均匀，加入到PVA溶液中，制备磷酸钙/PVA浆液；
将磷酸钙/PVA浆液倒入到聚氨酯泡沫中，经反应1～72h，干燥24h，将其制备成圆柱体，在烧结炉中，烧结温度为800～1250℃，烧结时间为3～36h，室温冷却，得到多孔陶瓷，其孔径为100～300μm；
(2)硫酸钙水泥的制备：配置含有吡咯喹啉醌的纤维素溶液，其中，吡咯喹啉醌占溶液的质量百分含量为0.5～5％，纤维素占溶液的质量百分含量为0.5～20％；
按照粉液质量比3:2将硫酸钙粉体和含有吡咯喹啉醌的纤维素溶液混合均匀，得到硫酸钙水泥；
(3)骨填充材料的制备：在成型磨具中，先注入占骨填充材料质量百分含量为30％的硫酸钙水泥，再将占骨填充材料质量百分含量为20～60％的多孔陶瓷放入到硫酸钙水泥中，再注入剩余的10～50％的硫酸钙水泥填满磨具并封口，对其加压5～35MPa，持续15～60min，将其取出固化12～36h，在5％RH环境下干燥3～24h得到圆柱体骨填充材料。
4.如权利要求3所述的制备方法，其特征在于，步骤(1)中的磷酸钙的粒径为50～150μm。
5.如权利要求3所述的制备方法，其特征在于，步骤(1)中的磷酸钙是锌磷灰石，锌磷灰石中，锌与锌钙的摩尔比为0.5～2:10。
6.如权利要求3所述的制备方法，其特征在于，步骤(1)中PVA粒径为100～300μm，PVA溶液中PVA的质量百分含量为1～5％。
7.如权利要求3所述的制备方法，其特征在于，步骤(1)中圆柱体尺寸为
8.如权利要求3所述的制备方法，其特征在于，步骤(2)中纤维素优选羟丙基纤维素，优选羟丙基纤维素占溶液的质量百分含量为10～20％，硫酸钙粒径为50～100μm。
9.如权利要求3所述的制备方法，其特征在于，步骤(3)中圆柱体骨填充材料尺寸为
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